Silicone hydrogel contact lens

ABSTRACT

The invention provides molds and mold inserts useful in the production of contact lenses. In particular, the invention provides high optical quality molds and inserts useful for manufacturing silicone hydrogel contact lenses.

FIELD OF THE INVENTION

The present invention relates to molds and mold inserts useful in theproduction of contact lenses. In particular, the invention provides highoptical quality molds and mold inserts for use in the manufacture ofsilicone hydrogel contact lenses.

BACKGROUND OF THE INVENTION

The use of soft contact lenses for reasons of cosmetics and for thecorrection of visual acuity is well known. Typically, these lenses aremanufactured by casting. The mold halves used in the casting of thelenses are produced by first machining metallic inserts and then usingthe inserts to produce the mold halves. The process of machining theinserts may cause periodic defects, or periodic structures, that may betransferred to the mold halves. The molding surfaces of the mold halvesare adequate to produce optical quality lenses for conventional hydrogellenses cast in the mold halves.

However, in the cast molding of silicone hydrogel lenses, the siliconehydrogel materials precisely replicate the mold surface. Thus, periodicstructures on the mold surface are transposed onto the lens' surface. Ifthe lens is coated with a swellable, or hydrophilic coating, theswelling of the coating magnifies these surface defects. These magnifieddefects may compromise the lens wearer's vision by generating coherentscattering (prismatic effect) or tool marks visible to the eye carepractitioner. Thus, the molds may produce coated silicone hydrogellenses with surfaces of less than optical quality. Therefore, a needexists for a method and materials to overcome this problem.

DESCRIPTION OF THE INVENTION AND ITS PREFERRED EMBODIMENTS

The present invention provides molds useful for cast molding siliconehydrogel contact lenses, inserts for producing the molds, and lensesmade using the molds of the invention. The molds of the invention havemolding surfaces on which periodic structures, resulting from themachining of the insert that forms the mold, are of an amplitude and aperiodicity less than that that results in production of optical defectson the lens surface that, when the lens is coated, will affect thewearer's vision.

In one embodiment, the invention provides a lens insert comprising,consisting essentially of, and consisting of at least one opticallycritical surface, wherein periodic structures on the optically criticalsurface are of a periodicity of less than about 3 μm and an amplitude ofless than about 4 nm RMS. In another embodiment, the invention providesa mold half for use in molding a contact lens, the mold half comprising,consisting essentially of, and consisting of at least one moldingsurface, wherein periodic structures on the molding surface are of aperiodicity of less than about 3 μm and an amplitude of less than about4 nm RMS. In yet another embodiment, the invention provides a siliconehydrogel contact lens comprising, consisting essentially of, andconsisting of at least one surface wherein periodic structures on thesurface are of a periodicity of less than about 3 μm and an amplitude ofless than about 4 nm RMS. For purposes of the invention, the amplitudemeasurement is made over a 50×50 μm area using Atomic Force Microscopy.

By “optically critical surface” is meant the surface of the mold insertused to produce the molding surface of a lens mold or mold half. By“molding surface’ is meant the surface of a mold or mold half used toform a surface of a lens.

The optically critical surface of the inserts of the invention arepreferably polished to randomize the surface structures and reduce theroughness to the desired levels. The inserts are first produced by anyconvenient method including, without limitation, by single, diamondpoint turning of a suitable material. Typically, the inserts are shapedusing a controlled-waviness, diamond cutting tool with as many as twofinish cuts using the same tool. One ordinarily skilled in the art willrecognize that a controlled-waviness tool is a tool that, no matter atwhat point on the cutting portion of the tool the cut is made, theradius at that point is that specified by the tool maker, withintolerances, with only minimal, local deviations. Such a tool providesthat the final part cut will be extremely accurate. The tool nose radiimay range from about 100 to 250 micrometers.

Polishing of the inserts to provide the optically critical surfaces ofthe invention may be carried out by any convenient method. Preferably,polishing is performed by using a heavy carbon diamond polishingcompound applied to a cloth and a jig shaped to match the insert radius.The insert and jig are placed into the polisher for an appropriateamount of time, for example about one minute, and then removed andswabbed with a suitable solvent, such as an alcohol, to remove thepolishing compound. The insert is then inspected and the processrepeated as necessary. The insert is finally inspected by any convenientmethod including, without limitation, by use of an interferometer, toensure that the radius meets the design specifications and that theperiodic structures are of the desired periodicity and amplitude.

As an alternative to polishing, lathing using conditions suitable toproduce the optically critical surfaces of the invention are selected sothat amplitude and periodicity of the periodic structures are within thedesired limits. For example, the ratio of linear feed rate, or the rateat which the diamond tool tracks across the surface of the part measuredin mm/min, to the spindle speed in rev./min is used that is sufficientto provide the desired increment between each lathe line or spiral. Toobtain lathe lines at 1 micron intervals, one uses 5 mm/min linear feedand 5,000 rpm, 10 mm/min linear feed and 10,000 rpm, or any figures thatprovide the ratio of 1/1000. To obtain lathe lines less than 300 nmapart, the appropriate ratio to be used is 3/10000 or a linear feed of2.4 mm/min with a spindle speed of 8000 rpm.

The inserts of the invention may be constructed of any material that canbe made with an optical finish including, without limitation, metal,quartz, ceramic, polymers, and the like. Suitable metals include,without limitation, pure steel, brass, copper, nickel-plated substrates,chromium, cobalt-nickel, alloyed martensitic steel, AMPCOLOY™substrates, and the like, and combinations thereof Preferably, theinserts are nickel-plated copper or nickel-plated brass. Examples ofuseful polymer materials include, without limitation, polycarbonates,cycloolefins, nylon, DELRIN®, TEFLON®, polystyrene, polypropylene,poly(acrylonitrile), and the like, and combinations thereof.

The inserts are used to form the molds or mold halves of the inventionusing any known method. Generally, the molds are cast from the inserts.Typically, an insert suitable for forming the molding surface of themold or mold half will be paired with a complementary insert to be usedto form the non-molding surface of the mold or mold half. The molds ofthe invention may be made from any material suitable for use in theproduction of contact lenses. Suitable mold materials include, withoutlimitation, polyolefins such as polypropylene, polystyrene, and cyclicpolyolefins, polyacrylonitrile materials and the like, and combinationsthereof.

The molds and inserts of the invention may be used to produce any typeof silicone hydrogel lens. The lenses of the invention are siliconehydrogel lenses, preferably silicone hydrogel lenses coated with aswellable coating. Suitable silicone hydrogel materials include, withoutlimitation, silicone hydrogels made from silicone macromers such as thepolydimethylsiloxane methacrylated with pendant hydrophilic groupsdescribed in U.S. Pat. Nos. 4,259,467; 4,260,725 and 4,261,875; or thepolydimethylsiloxane macromers with polymerizable functional describedin U.S. Pat. Nos. 4,136,250; 4,153,641; 4,189,546; 4,182,822; 4,343,927;4,254,248; 4,355,147; 4,276,402; 4,327,203; 4,341,889; 4,486,577;4,605,712; 4,543,398; 4,661,575; 4,703,097; 4,837,289; 4,954,586;4,954,587; 5,346,946; 5,358,995; 5,387,632; 5,451,617; 5,486,579;5,962,548; 5,981,615; 5,981,675; and 6,039,913. They may also be madeusing polysiloxane macromers incorporating hydrophilic monomers such asthose described in U.S. Pat. Nos. 5,010,141; 5,057,578; 5,314,960;5,371,147 and 5,336,797; or macromers comprising polydimethylsiloxaneblocks and polyether blocks such as those described in U.S. Pat. Nos.4,871,785 and 5,034,461. All of the cited patents are herebyincorporated in their entireties by reference.

Suitable materials may also be made from combinations of oxyperm andionoperm components such as is described in U.S. Pat. Nos. 5,760,100;5,776,999; 5,789,461; 5,807,944; 5,965,631 and 5,958,440. Hydrophilicmonomers may be incorporated into such copolymers, including2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate “HEMA”),N,N-dimethylacrylamide (“DMA”), N-vinylpyrrolidone,2-vinyl-4,4′-dimethyl-2-oxazolin-5-one, methacrylic acid, 2-hydroxyethylmethacrylamide. Additional siloxane monomers may be incorporated such astris(trimethylsiloxy)silylpropyl methacrylate, or the siloxane monomersdescribed in U.S. Pat. Nos. 5,998,498; 3,808,178; 4,139,513; 5,070,215;5,710,302; 5,714,557 and 5,908,906. They may also include varioustoughening agents, tints, UV blockers and wetting agents. They can bemade using diluents such as primary alcohols, or the secondary ortertiary alcohols described in U.S. Pat. No. 6,020,445. All of the citedpatents are hereby incorporated in their entireties by reference.

In a preferred embodiment, the lenses of the invention are made byreacting a macromer with a reaction mixture that includes silicone basedmonomers and hydrophilic monomers. The macromers may be made bycombining a methacrylate or an acrylate and a silicone in the presenceof a Group Transfer Polymerization (“GTP”) catalyst. These macromerstypically are copolymers of various monomers. They may be formed in sucha way that the monomers come together in distinct blocks, or in agenerally random distribution. These macromers may furthermore belinear, branched, or star shaped. Branched structures are formed forinstance if polymethacrylates, or crosslinkable monomers such as3-(trimethylsiloxy)propyl methacrylate are included in the macromer.

Initiators, reaction conditions, monomers, and catalysts that can beused to make GTP polymers are described in “Group-TransferPolymerization” by O. W. Webster, in Encyclopedia of Polymer Science andEngineering Ed. (John Wiley & Sons) p. 580, 1987. These polymerizationsare conducted under anhydrous conditions. Hydroxyl-functional monomers,like HEMA, may be incorporated as their trimethylsiloxy esters, withhydrolysis to form free hydroxyl groups after polymerization. GTP offersthe ability to assemble macromers with control over molecular weightdistribution and monomer distribution on the chains. This macromer maythen be reacted with a reaction mixture of predominantlypolydimethylsiloxane (preferably, monomethacryloxypropyl terminatedpolydimethylsiloxane (“mPDMS”), and hydrophilic monomers. PreferredmPDMS is of the formula:

wherein b=0 to 100, preferably 8 to 10; R₅₈ is a monovalent groupcontaining a ethylenically unsaturated moiety, preferably a monovalentgroup containing a styryl, vinyl, or methacrylate moiety, morepreferably a methacrylate moiety; each R₅₉ is independently a monovalentalkyl, or aryl group, which may be further substituted with alcohol,amine, ketone, carboxylic acid or ether groups, preferably unsubstitutedmonovalent alkyl or aryl groups, more preferably methyl; and R₆₀ is amonovalent alkyl, or aryl group, which may be further substituted withalcohol, amine, ketone, carboxylic acid or ether groups, preferablyunsubstituted monovalent alkyl or aryl groups, preferably a C₁₋₁₀aliphatic or aromatic group which may include hetero atoms, morepreferably C₃₋₈ alkyl groups, most preferably butyl, particularlysec-butyl group.

Preferred macromer components include mPDMS, 3-methacryloxypropyltris(trimethylsiloxy) silane (“TRIS”), methyl methacrylate, HEMA, DMA,methacrylonitrile, ethyl methacrylate, butyl methacrylate,2-hydroxypropyl-1-methacrylate, 2-hydroxyethyl methacrylamide andmethacrylic acid. It is even more preferred that the macromer is madefrom a reaction mixture of that HEMA, methyl methacrylate, TRIS, andmPDMS. It is most preferred that macromer is made from a reactionmixture comprising, consisting essentially of, or consisting of about19.1 moles of the HEMA, about 2.8 moles of methyl methacrylate, about7.9 moles of TRIS, and about 3.3 moles of mono-methacryloxypropylterminated mono-butyl terminated polydimethylsiloxane, and is completedby reacting the aforementioned material with about 2.0 moles per mole of3-isopropenyl-ω,ω-dimethylbenzyl isocyanate using dibutyltin dilaurateas a catalyst.

The reactive components of silicone hydrogels typically are acombination of hydrophobic silicone with very hydrophilic components.Because these components are often immiscible due to their differencesin polarity, it is particularly advantageous to incorporate acombination of hydrophobic silicone monomers with hydrophilic monomers,especially those with hydroxyl groups, into the macromer. The macromercan then serve to compatibilize the additional silicone and hydrophilicmonomers that are incorporated in the final reaction mixture. Theseblends typically also contain diluents to further compatibilize andsolubilize all components. Preferably, the silicone based hydrogels aremade by reacting the following monomer mix: macromer; an Si₇₋₉monomethacryloxy terminated polydimethyl siloxane; and hydrophilicmonomers together with minor amounts of additives and photoinitiators.It is more preferred that the hydrogels are made by reacting macromer;an Si₇₋₉ monomethacryloxy terminated polydimethyl siloxane; TRIS; DMA;HEMA; and tetraethyleneglycol dimethacrylate (“TEGDMA”). It is mostpreferred that the hydrogels are made from the reaction of (all amountsare calculated as weight percent of the total weight of the combination)macromer (about 18%); an Si₇₋₉ monomethacryloxy terminated polydimethylsiloxane (about 28%); TRIS (about 14%); DMA (about 26%); HEMA (about5%); TEGDMA (about 1%), polyvinylpyrrolidone (“PVP”) (about 5%); withthe balance comprising minor amounts of additives and photoinitiators,and that the reaction is conducted in the presence of 20% wtdimethyl-3-octanol diluent.

The lenses' surfaces may be coated with a swellable coating by anyconvenient method such as by application of a suitable hydrophiliccoating. The coatings may be applied by any convenient method. Preferredhydrophilic coatings include, without limitation, poly(acrylic acid),poly(methacrylic acid), poly(maleic acid), poly(itaconic acid),poly(acrylamide), poly(dimethacrylamide), block or random copolymers of(meth)acrylic acid, acrylic acid, maleic acid, itaconic acid with anyreactive vinyl monomer, carboxymethylated polymers, such ascarboxymethylcellulose, dextran, polyvinyl alcohol, polyethylene oxide,poly(HEMA), polysulfonates, polysulfates, polylactam, polyglycolic acid,polyamines, and the like, and mixtures thereof More preferably, thecoating is poly(acrylic acid), poly(methacrylic acid),poly(dimeth)acrylamide, poly(acrylamide), or poly(HEMA). Mostpreferably, poly(acrylic acid), poly(acrylamide), or poly(HEMA) is used.

The lenses of the invention may be made using any known process forcontact lens production. Preferably, the lenses are made by photocuringthe lens composition and applying a coating to the cured lens. Variousprocesses are known for molding the reaction mixture in the productionof contact lenses, including spincasting and static casting. Thepreferred method for producing contact lenses of this invention is bythe direct molding of the silicone hydrogels, which is economical, andenables precise control over the final shape of the hydrated lens. Forthis method, the reaction mixture is placed in a mold having the shapeof the final desired silicone hydrogel, i.e. water-swollen polymer, andthe reaction mixture is subjected to conditions whereby the monomerspolymerize, to produce a polymer in the approximate shape of the finaldesired product. The conditions for such polymerization are well knownin the art. The polymer mixture optionally may be treated with a solventand then water, producing a silicone hydrogel having a final size andshape similar to the size and shape of the original molded polymerarticle. This method can be used to form contact lenses and is furtherdescribed in U.S. Pat. Nos. 4,495,313, 4,680,336, 4,889,664 and5,039,459 incorporated herein by reference in their entireties.

The invention will be clarified further by consideration of thefollowing, non-limiting examples.

EXAMPLES 1-18 Insert and Mold Fabrication

Inserts were fabricated from brass by diamond point turning using acontrolled waviness tool nose. Unless otherwise noted, all brass insertswere cut with 4 semi-finished cuts, cutting depth=0.25 mm, at a spindlespeed of 8,000 rpm and feed rate of 25 mm/min. The inserts then werecut, cutting depth=0.005 mm, at a spindle speed of 8,000 rpm and feedrate of 5 mm/min. The inserts then were: 1.) untreated; 2.) treated witha thin nickel coating of approximately 2-4 μm applied to the insertsurface by evaporation; 3.) treated with a thick nickel coating ofapproximately 100-200 μm applied to the insert surface by evaporation;or 4.) polished using diamond polishing paste.

For examples 1-18, lens mold halves were injection molded from TOPAS®polymer using the inserts listed on the Table below. The inserts wereinstalled into an 8-cavity injection mold and molten TOPAS®, atapproximately 290-300° C., injected into the mold under pressure. Thepressure was relieved, the molds allowed to cool, opened, and the moldsejected.

Lens Formation—Examples 1-18

Macromer for use in producing lenses was prepared by adding 191.75 g1-trimethylsiloxy-1-methoxy-2-,ethylpropene to a 13.75 ml of a 1Msolution of tetrabutyl ammonium-m-chlorobenzoate (“TBACB”) intetrahydrofuran (“THF”), 30.0 g bis(dimethylamino)methylsilane, 61.39 gp-xylene, 154.28 g methyl methacrylate, and 1892.13 g2-(trimethylsiloxy)ethyl methacrylate in 4399.78 g THF at 14° C. under anitrogen atmosphere. 30 ml of additional TBACB in THF (0.40 M) wereadded over a period of 260 minutes, during which time the reactionmixture was allowed to exotherm, and then cooled to 30° C. Sixty minutesafter addition of 2-(trimethylsiloxy)ethyl methacrylate, a solution of467.56 g 2-(trimethylsiloxy)ethyl methacrylate, 3636.6 g mPDMS and3673.84 g TRIS and 20.0 g bis(dimethylamino)methylsilane was added, andthe mixture was allowed to exotherm and then cooled to 30° C. for 2hours. A solution of 10.0 g bis(dimethylamino)methylsilane, 154.26 gmethyl methacrylate, and 1892.13 g 2-(trimethylsiloxy)ethyl methacrylatewas then added and the mixture was again allowed to exotherm. After 2hours, 2 gallons of anhydrous THF was added, followed by a solution of439.69 g water, 740.6 g methanol and 8.8 g dichloroacetic acid after thesolution was allowed to cool down to 34° C. The mixture was refluxed for4.5 hours, heating with an oil bath at110° C., and volatiles weredistilled off at 135° C., with addition of toluene to aid in removal ofwater, until a vapor temperature of 110° C. is reached.

The reaction flask was cooled to 110° C., and a solution of 443 gdimethyl meta-isopropenyl benzyl isocyanate and 5.7 g dibutyltindilaurate was added. The mixture was reacted for 3.5 hours, then cooledto 30° C. The toluene was evaporated under reduced pressure to yieldoff-white, anhydrous, waxy, reactive macromer.

Silicone hydrogel lenses were made using a mixture of the macromer withthe following: 14 wt percent TRIS; 26 wt percent DMA; 28 wt percentmPDMS; 2 wt percent NORBLOC™; 1 wt percent TEGDMA; 5 wt percent HEMA;and 8 wt percent PVP, along with minor amounts of additives anddiluents. The following procedure was used to form lenses.

Contact lenses were formed by adding approximately 0.10 g of the lensmaterial to TOPAS® mold cavities and the material was cured forapproximately 1200 sec. Polymerization was carried out under a nitrogenpurge and was photointiated with 5 mW cm² of ultraviolet light generatedwith an Andover Corp. 420PS10-25 AM39565-02 light filter. After curingwas completed, the molds were opened, the lenses released into a 1:1blend of water and isopropanol, and leached in isopropanol to removeresidual monomers and diluent. The lenses were equilibrated inphysiological borate-buffered saline. Coated lenses were prepared byimmersing the leached lenses in a solution of 1.0% of 250,000 MWpoly(acrylic acid) in borate-buffered saline at 45° C. to which 0.1% of1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride was added.After stirring for approximately 30 min the lenses were rinsed inborate-buffered saline solution.

Lens Testing

In vitro tool marks were determined for all lenses by blotting each lensdry and placing the lens on a steel, 44.75D (7.55 mm radius) keratometercalibration standard and using a Zeiss slit lamp (Model 30SL/M withpower supply 31 04 58) with 16-40× magnification at maximum illuminationto look for the presence or absence of tool marks. In addition to thelenses for Examples 1-18, examples 19 and 20, FOCUS® NIGHT & DAY dailywear lens made of lotrafilcon A, uncoated and coated, respectively, withpoly(acrylic acid) were tested. The following table lists the results ofthe study.

Lens Tool Mark/Primsatic Example Lens Power (D) Insert/Lens Effect Rate1 −4.00 Polished brass/PAA 0% (0/5) coated 2 −2.50 Unpolished brass/PAA60% (3/5) coated 3 −2.50 Polished brass/PAA 0% (0/5) coated 4 −2.00Unpolished brass/PAA 100% (5/5) coated 5 −2.00 Polished brass/PAA 0%(0/5) coated 6 −2.50 Unpolished brass/PAA 60% (3/5) coated 7 −2.50Polished brass/PAA 0% (0/5) coated 8 −4.00 Unpolished brass/PAA 100%(5/5) coated 9 −2.50 Thin Ni coated 100% (5/5) brass/PAA coated 10 −4.00Thin Ni coated 100% (5/5) brass/PAA coated 11 −2.50 Thick Ni coated 100%(10/10) brass/PAA coated 12 −4.00 Thick NI coated 14% (117) brass/PAAcoated 13 −2.50 Polished brass/PAA 100% (10/10) coated 14 −4.00 Polishedbrass/PAA 0% (0/10) coated 15 −4.00 Unpolished Brass 0% (0/5) Toolingfeed speed 7.5 mm/min @ 5000 rpm/Uncoated 16 −4.00 Unpolished Brass 100%(10/10) Tooling feed speed 7.5 mm/min @ 5000 rpm/PAA Coated 17 −4.00Unpolished Brass 0% (0/5) Tooling feed speed 5 mm/min @ 8000rpm/Uncoated 18 −4.00 Unpolished Brass 100% (10/10) Tooling feed speed 5mm/min @ 8000 rpm/PAA Coated 19 −1.00 Uncoated 0% (0/2) 20 −1.00 PAACoated 50% (1/2)

1. A silicone hydrogel contact lens, comprising at least one surfacewherein periodic structures on the surface are of a periodicity of lessthan about 3 μm and an amplitude of less than about 4 nm RMS.
 2. Thesilicone hydrogel lens of claim 1, wherein the at least one surfacefurther comprises a hydrophilic coating.
 3. The silicone hydrogel lensof claim 2, wherein the hydrophilic coating is selected from the groupconsisting of poly(acrylic acid), poly(methacrylic acid),poly(dimeth)acrylamide, poly(acrylamide), orpoly(hydroxyethylmethacrylate).
 4. The silicone hydrogel lens of claim2, wherein the hydrophilic coating is poly(acrylic acid).
 5. Thesilicone hydrogel lens of claim 2, wherein the hydrophilic coating ispoly(acrylamide).
 6. The silicone hydrogel lens of claim 2, wherein thehydrophilic coating is poly(hydroxyethylmethacrylate).
 7. The siliconehydrogel lens of claim 1, wherein the silicone hydrogel comprises aGroup Transfer Polymerization product of a reaction mixture comprising2-hydroxyethyl methacrylate, methyl methacrylate,methacryloxypropyltris(trimethylsiloxy)silane, andmono-methacryloxypropyl terminated mono-butyl terminatedpolydimethylsiloxane and a polymerizable mixture comprising a Si₇₋₉monomethacryloxy terminated polydimethyl siloxane; a methacryloxypropyltris(trimethyl siloxy) silane; N,N-dimethyl acrylamide; 2-hydroxy ethylmethacrylate; and tetraethyleneglycol dimethacrylate.
 8. The siliconehydrogel lens of claim 2, wherein the silicone hydrogel comprises aGroup Transfer Polymerization product of a reaction mixture comprising2-hydroxyethyl methacrylate, methyl methacrylate,methacryloxypropyltris(trimethylsiloxy)silane, andmono-methacryloxypropyl terminated mono-butyl terminatedpolydimethylsiloxane and a polymerizable mixture comprising a Si₇₋₉monomethacryloxy terminated polydimethyl siloxane; a methacryloxypropyltris(trimethyl siloxy) silane; N,N-dimethyl acrylamide; 2-hydroxy ethylmethacrylate; and tetraethyleneglycol dimethacrylate.
 9. The siliconehydrogel lens of claim 1, wherein the silicone hydrogel comprises afluorosiloxane hydrogel.
 10. The silicone hydrogel lens of claim 2,wherein the silicone hydrogel comprises a fluorosiloxane hydrogel.